Laser glass host compositions comprising TeO{HD 2{B , La{hd 2{b O{HD 3 {B and ZnO

ABSTRACT

Laser glass compositions are disclosed that provide laser articles with increased efficiency, the compositions comprising TeO2, La2O3 and ZnO in certain molar amounts, as defined by certain areas set forth in a ternary diagram of the FIGURE, the laser glass compositions also including an effective lasing amount of Nd2O3. Also disclosed are methods of making highly efficient glass laer articles, such as rods, discs and the like, the methods including the steps of: 1. MELTING LASER GLASS BATCH-FORMING MATERIALS TO PROVIDE MOLTEN GLASS COMPRISING CERTAIN MOLAR AMOUNTS OF TeO2, La2O3 and ZnO, the molten glass capable of being a host for an effective lasing amount of Nd2O3; 2. forming a glass laser blank from the molten glass; and 3. FABRICATING A LASER ARTICLE FROM THE GLASS BLANK, THE ARTICLE HAVING INCREASED LASING EFFICIENCY. Also disclosed is the new use of a TeO2/La2O3/ZnO glass host composition as a glass laser article in which the proportions of TeO2, La2O3 and ZnO are present in certain molar amounts as above-described, and in which the glass composition is a host for an effective lasing amount of Nd2O3, the new use including the steps of: 1. FORMING A LASER ARTICLE FROM THE GLASS COMPOSITION ABOVEDESCRIBED; 2. PUMPING THE LASER ARTICLE TO CAUSE AN ENERGY INVERSION; AND 3. PASSING MONOCHROMATIC LIGHT THROUGH THE ARTICLE TO CAUSE STIMULATED EMISSION AT A WAVELENGTH OF ABOUT 1.06 MICRONS.

United States Patent [1 1 Cooley l l LASER GLASS HOST COMPOSlTIONS COMPRISING TEO LA O AND ZNO [75] Inventor: Richard F. Cooley, Toledo. Ohio [731 Assignee: Owens-Illinois, Inc., Toledo. Ohio [22] Filed: June 27, 1973 [211 App]. No.: 374,229

[52] US. Cl. 106/47 R; 106/47 Q; 252/301.4 F; 252/30l.6 R; 252/30l.6 F

[51] Int. Cl. C03c 3/28 [58] Field of Search. 252/301.6 S, 301.4 S, 301.4 F, 252/3014 R; 106/47 Q, 47 R Primary Examiner-Winston A. Douglas Assistant Examiner-John F. Niebling Attorney, Agent, or FirmRichard D. Heberling; E. J. Holler [57] ABSTRACT Laser glass compositions are disclosed that provide laser articles with increased efficiency, the composi tions comprising TeO La O and ZnO in certain May 13, 1975 molar amounts, as defined by certain areas set forth in a ternary diagram of the FIGURE, the laser glass compositions also including an effective lasing amount of Nd O Also disclosed are methods of making highly efiicient glass laer articles, such as rods, discs and the like, the methods including the steps of:

1. melting laser glass batch-forming materials to provide molten glass comprising certain molar amounts of "1e0 La o and ZnO, the molten glass capable of being a host for an effective lasing amount of Nd O 2. forming a glass laser blank from the molten glass; and

3. fabricating a laser article from the glass blank, the article having increased lasing efficiency,

Also disclosed is the new use of a TeO /La O /ZnO glass host composition as a glass laser article in which the proportions of TeO La O and ZnO are present in certain molar amounts as above-described, and in which the glass composition is a host for an effective lasing amount of Nd O the new use including the steps of:

1. forming a laser article from the glass composition above-described;

2. pumping the laser article to cause an energy inversion; and

3. passing monochromatic light through the article to cause stimulated emission at a wavelength of about 1.06 microns.

14 Claims, 1 Drawing Figure LASER GLASS HOST COMPOSITIONS COMPRISING T La o AND ZnO This invention relates to laser glass compositions comprising a glass host containing TeO La- O and ZnO in certain molar amounts, the laser glass being a host for an effective lasing amount of M 0 The present invention also relates to methods of making the laser glass compositions including forming outstanding laser glass articles from the compositions. The present invention also relates to the new use for a glass laser composition in which the glass contains certain molar amounts of TeO La O and ZnO and in which the glass composition is a host for an effective lasing amount of M1 0 the new use including the stepsof:

l. forming a laser article from the glass composition containing TeO La O and ZnO;

2. pumping the resultant laser article to cause an energy inversion; and

3. lasing the pumped article.

It is highly desirable to provide laser glass compositions that can be used to make outstanding highlyefficient glass laser articles. It is also desirable to provide methods for making the laser articles and the new use for glass compositions comprising TeO La O and ZnO, in which the new use includes the steps of:

l. forming a glass laser article from the abovedescribed glass composition that is a host for an effective lasing amount of Nd O 2. pumping the laser article; and thereafter 3. lasing the pumped article.

It is an object of the present invention to provide a laser glass composition comprising TeO La O- and ZnO in which the proportions in molar amounts of TeO La O and ZnO are defined by the area within the heavy lines connecting the points ABCD of the ternary diagram of the Figure, and in which the glass is a host for an effective lasing amount of M1 0 It is an object of the present invention to provide a laser glass composition that makes highlyefficient laser articles, the composition comprising a host glass con taining Te0 La O and ZnO, with certain molar amounts that are defined by the area connecting the points EFGH in the ternary diagram, the host glass containing an effective lasing amount of Nd O It is an object of the present invention to provide a method for making a glass laser article comprising the steps of:

1. melting laser glass batch-forming materials to provide a molten glass comprising TeO- La O and ZnO, in which the proportions thereof, in moles, are defined by the area within the heavy lines connecting the points ABCD of the ternary diagram, and an effective lasing amount of Nd O 2. forming a glass laser blank from the molten glass;

and

3. fabricating the laser article from the glass blank.

It is an object of the present invention to provide a method for making highly-efiicient glass laser articles such as rods and discs, etc., the method comprising the steps of;

]. melting laser glass batch-forming materials to provide a molten glass containing TeO La o and ZnO,

in which the proportions thereof are defined by the area within the heavy lines connecting the points EFGH of the ternary diagram, the molten glass capable of functioning as a host for an effective lasing amount of Nd O 2. forming a glass laser blank from the molten glass; and

3. fabricating a laser article from the glass blank.

It is an object of the present invention to provide the new use for a TeO /La O /ZnO glass composition as a glass laser article in which the proportions of TeO- lea- 0 and ZnO are defined in a general range by the area within the heavy lines connecting the points ABCD and are defined in a preferred range within the heavy lines connecting the points EFGH of the ternary diagram of the Figure of the drawings, and in which the glass composition is a host for an effective lasing amount of Nd O the new use comprising the steps of:

l. forming a laser article from the glass composition above-described;

2. pumping the laser article to cause an energy inversion; and

3. passing monochromatic light through the article to cause stimulated emission at a wavelength of about L06 microns.

It is an object of the present invention to provide a glass laser article made by forming a glass laser blank from molten glass comprising TeO LaO and ZnO, the molar proportions of TeO La O and ZnO being defined by the area within the heavy lines connecting the points ABCD of the ternary diagram of the Figure, and in which the molten glass is capable of being a host for an effective lasing amount of Nd O and fabricating a laser article from the glass laser blank, the article having increased lasing efficiency.

These and other objects will be apparent from.the specification that follows, the appended claims, and the drawings, in which the Figure is a ternary diagram of the glass host composition of the present invention in which the molar proportions of TeO La O and ZnO are defined by the area within the heavy lines of the ternary diagram.

The present invention provides laser glass host compositions for making outstanding laser glass articles, the host compositions containing an effective lasing amount of Nd O and comprising TeO La O and ZnO in certain molar amounts that are defined in a general range by the area within the heavy lines connecting the points ABCD of the ternary diagram of the Figure of the drawings. The preferred range of the molar amounts of TeO La o and ZnO are defined by the area within the heavy lines connecting the points EFGH of the ternary diagram.

The present invention provides a laser glass composition comprising:

1. a host glass containing about 65-898 mole percent TeO about 0.28 mole percent La O and about l0-34.8 mole percent ZnO; and

2. an effective lasing amount of Nd O The present invention also provides a laser glass host composition comprising about 67-878 mole percent TeO about 0.2-6 mole percent La,O and about l232.8 mole percent ZnO, the host composition containing about 0.0ll .5 mole percent Nd O The present invention also provides methods for making efficient glass laser articles, such as rods or discs, the methods including:

l. melting laser glass batch-forming materials to provide a moltenglass comprising TeO La O and ZnO, in which the molar amounts thereof are defined in a general range by the area within the heavy lines connecting the points ABCD of the ternary diagram of the Figure, and in which the molten glass is capable of being a host for an effective lasing amount of Nd O patent), and at least about 50% over that of a lithiacalcia-alumino silicate glass laser rod as set forth, for instance, in U.S. Pat. No. 3,471,409, to Lee and Rapp, the laser rod being of the following composition:

2. forming a glass blank from the molten glass; and 5 3. fabricating the outstanding laser article from the blank.

The present invention also provides the new use for lngrediems Mole Pelcem a glass composition as a highly efficient glass laser artis c e cle in which the glass comprises TeO La O and ZnO, 10 12 3 and in which composition the molar amounts of TeO E3 a0 10 La O and ZnO are defined In a general range within Ndzoa 05 the area formed by the heavy lines connecting the points ABCD of the ternary diagram, and in which the glass compgsitign i a h f an effe i l i 15 In general, the highest fluorescent intensity value for amount of M1 0 h new use wmprising h steps f; a zinc tellurite glass, as above-described, containing 35 1 formin a l ss l s r ti l fr th glass compomole percent ZnO, is about 2.09 when compared to the sition comprising TeO La O and ZnO i h an ff fluorescent intensity value of the above-described i 1 m amount f 1 0 lithia-calcia-alumino silicate glass laser, which is the 2. pumping the laser article to provide an energy inmference glass arbitrarily held to be version; and The following examples are intended to illustrate the 3 lasing the pumped laser m present invention and not to limit the same in any way. A zinc tellurite glass consisting essentially of a major EXAMPLE 1 molar proportion of T302 and about 20 to 40 molar percent of ZnO is described in the Redman U.S. Pat. PART A No. 3,423,326. These zinc tellurite glasses were re- A 15 gram melt was prepared by mixing reagent ported as having some fluorescent activity when doped grade raw materials, in the following molar percent and with M1 0 also for convenience, weight percent, with ml. of

As previously indicated, the outstanding laser glass 30 water,

Ingredients Mole Percent Weight Percent Host Glass Laser Article Host Glass Laser Article Tco 85.0 34.3 87.4 85.9 ZnO 12.0 11.9 6.3 6.2 1.11 0, 3.0 3.0 6.3 6.2 M1 0, 0.8 1.7

0 host compositions of the present inventlon unexpect- The slurry was mixed for 10 minutes and poured into edly exhibit much higher fluorescent activity than the a gold crucible. The crucible was placed in an air circuzinc tellurite glasses of the Redman patent, the inlating oven with the temperature maintained at 110C. creased fluorescent activity indicating a greater lasing overnight to remove the water. The crucible was then efficiency for laser articles made from the host compoplaced in an electric resistance furnace with the temsitions of the present invention. As previously deperature at 750C. for 3 hours, or until homogenous, scribed, only certain molar proportions of TeO La O after which the molten glass immediately poured into and ZnO can be used to provide highly efficient glass apreheated 260C.) graphite mold forming adisc havlaser rods and discs. The increase in fluorescent activity ing an 1 H16 nch diameter and A inch thickness. The is generally at least about and preferably at least 50 graphite mold was placed in an annealing oven mainabout 60 or 70% over any of the zinc tellurite glasses mined at 3 0C. Aft r 1 hour, at 340C, the temperaof the Redman patent. The increase is at least 100% W 0f th an aling Oven was lowered at a rate of he a d t th wo kin a l f the Red- 38C. per hour to 250C. after which the annealing man patent oven was turned off and the mold cooled to room tem- There is no mention of any glass system in the Red- Pefamffl man patent other than a glass host composition consist- The Solid, annealed glass disc was removed from the ing essentially of tellurium oxide and zinc oxide. There mold wet ground and Polished with Close mlemflce is no suggestion in [he Redman patent that eff: a thickness Of 0.195 inches and a diameter Of ciem |aser articles can b d f m a h gmposiinches. The refractive index of the finished polished tion containing certain molar proportions of TeO 31355 disc was measured t0 be La O and ZnO.

In accordance with the present invention, increased PART B lasing efficiency is obtained for glass laser rods and The polished glass disc from Part A was tested for fludiscs.The increase in fluorescent activity is surprisingly orescence intensity and decay time in a high power greater in that the articles of the present invention expulsed test system. The disc was placed in a holder and hibit an activity of at least about 50% over that of a zinc tellurite glass containing approximately 65 mole percent TeO and 35 mole percent ZnO (see the Redman exposed to a beam of light from an EC & G model FX 12-25 xenon flash lamp. The flash lamp had a flash duration of about 20 microseconds. The disc was not observed to solarize after repeated excitation by the flash lamp. The fluorescence intensity and decay time of the excited sample was measured by photographing the oscilloscope display of the 1060 nanometer fluorescent 6 EXAMPLE 3 Part A A gram melt was prepared and polished glass discs prepared therefrom as described in Part A of Example intensity versus time on a Tektronix Model 556, Dual 5 Trace oscilloscope connected to an RCA S-l photo- 1, FP the molar welght Percentages of the raw multiplier, having a narrow band pass filter. mateflals were as follows:

Ingredients Mole Percent Weight Percent Host Glass Laser Article Host Glass Laser Article TeO, 75.0 74.4 78.4 77.2

ZnO 20.0 19.8 10.8 10.5

Fl (corrected) Fl (normalized) W The corrected fluorescence intensity was 1.74. The flu- Ingredients The refractive index of the finished polished glass disc was measured to be 2.07.

Part B The polished glass disc from Part A was tested for fluorescence intensity and decay time as described in Part B of Example 1. The normalized fluorescence intensity was 3.26 and the corrected fluorescence intensity was 1.85. The fluorescence decay time was 140 microseconds.

EXAMPLE 4 Part A A 15 gram melt was prepared and polished glass discs prepared therefrom as described in Part A of Example 1, except the molar or weight percentages of the raw materials were as follows:

Mole Percent Weight Percent Te0 ZnO La,O M1 0,

Host Glass Laser Article Host Glass Laser Article orescence decay time was 138 microseconds.

EXAMPLE 2 Part A A 15 gram melt was prepared and polished glass discs prepared therefrom as described in Part A of Example 1, except the molar or weight percentages of the raw materials were as follows:

The refractive index of the finished polished glass disc was measured to be 2.06.

Part B The polished glass disc from Part A was tested for fluorescence intensity and decay time as described in Part B of Example 1. The normalized fluorescence intensity was 3.53 and the corrected fluorescence intensity was 1.87. The fluorescence decay time was 140 microseconds.

Ingredients Mole Percent Weight Percent Host Glass Laser Article Host Glass Laser Article TeO 77.0 76.4 77.5 76.1 ZnO 16.0 15.9 8.3 8.1 La,O 7.0 6.9 14.2 14.1 NdgOf 0.8 1.7

The refractive index of the finished polished glass disc was measured to be 2.08.

Part B Other specific compositions disclosed herein as being suitable for use in the laser compositions of the present invention can be substituted for the specific laser compositions used in the working examples to provide substantially equivalent results. For instance. any of the host compositions set forth within the area formed by the heavy lines connecting the points ABCD of the ternary diagram can be used in place of any of the specific laser compositions used in the working examples. Thus, a host glass comprising about mole percent TeO 27 mole percent ZnO and 3 mole percent La,O can be used for the specific host composition set forth in Example 1. Likewise, a laser glass host composition comprising about 72 mole percent TeO 3 mole percent La O and 25 mole percent ZnO, as well as a glass host comprising about 68 mole percent TeO about 7 mole percent La O- and about 25 mole percent ZnO can be used in place of the host composition of Example 1 to provide substantially equivalent results.

What is claimed is:

l. A laser glass composition comprising TeO 1421 and ZnO. the proportions of TeO La O and ZnO in molar amounts being defined by the area within the heavy lines, connecting the points ABCD of the ternary diagram of the Figure, the laser glass composition including an effective lasing amount of Nd O for stimulated emission at a wavelength of about 1.06 microns.

2. A laser glass composition as defined in claim 1 in which the proportions of TeO La O and ZnO are within the area formed by the heavy lines connecting the points EFGH in the ternary diagram of the Figure of the drawing.

3. A laser glass composition consisting essentially of:

i. a host glass containing about (SS-89.8 mole percent TeO about 0.28 mole percent 1.21 0 and about l()34.8 mole percent ZnO', and

2. an effective lasing amount of Nd O 4. A laser glass host consisting essentially of about 67-878 mole percent TeO about 0.26 mole percent La O and about l232.8 mole percent ZnO, the host composition containing about 0.011.5 mole percent Nd O 5. A laser glass composition as defined in claim 3 in which the host glass comprises about 70 mole percent TeO 27 mole percent ZnO, and 3 mole percent La O 6. A laser glass composition as defined in claim 3 in which the glass host comprises about 72 mole percent TeO 3 mole percent La O and 25 mole percent ZnO.

7. A laser glass composition as defined in claim 3 in which the glass host comprises about 68 mole percent TeO about 7 mole percent La O and about 25 mole percent ZnO.

8. A method for making a glass laser article such as a rod, disc and the like, the method comprising the steps of:

l. melting laser glass batch-forming materials to provide a molten glass comprising TeO La O and ZnO in which the proportions thereof are defined by the area within the heavy lines connecting the points ABCD of the ternary diagram of the Figure of the drawings, and an effective lasing amount of Nd O for stimulated emission at a wavelength of about 1.06 microns;

2. forming a glass blank from the molten glass; and

3. fabricating a laser article from the glass blank, the

article having increased lasing efficiency.

9. A method as defined in claim 8 in which the glass comprising TeO La O and ZnO has amounts thereof defined by the area within the triangle connecting the points EFGH of the ternary diagram of the Figure of the drawing.

10. The new use for a TeO /La O /ZnO glass composition as a glass laser article in which the proportions of the heavy lines connecting the points ABQD in the ternary diagram in the Figure of the drawings and in which the glass composition is a host for an effective lasing" amount of Nd O the new use comprising the steps of: 1. forming a laser article from the glass composition defined in claim 1',

2. pumping the laser article to cause an energy inversion; and

3. passing monochromatic light through the article to cause stimulated emission at a wavelength of about 1.06 microns.

11. A laser glass article made from the composition defined in claim 1.

12. An article as defined in claim 11 in the form of a rod.

13. An article as defined in claim 1] in the form of a disc.

14. A laser glass article made according to the composition defined in claim 1 in which the laser glass composition has the proportions of TeO La,O and ZnO that are within the area formed by the heavy lines connecting the points EFGH in the ternary diagram of the figure of the drawing. 

1. A LASER GLASS COMPOSITION COMPRISING TEO2, LA2O3 AND ZNO, THE PROPORTIONS OF TEO2, LA2O3 AND ZNO IN MOLAR AMOUNTS BEING DEFINED BY THE AREA WITHIN THE HEAVY LINES, CONNECTING THE POINTS ABCD OF THE TERNARY DIAGRAM OF THE FIGURE, THE LASER GLASS COMPOSITION INCLUDING AN EFFECTIVE
 2. A laser glass composition as defined in claim 1 in which the proportions of TeO2, La2O3 and ZnO are within the area formed by the heavy lines connecting the points EFGH in the ternary diagram of the Figure of the drawing.
 2. an effective lasing amount of Nd2O3.
 2. forming a glass blank from the moltEn glass; and
 2. pumping the laser article to cause an energy inversion; and
 3. passing monochromatic light through the article to cause stimulated emission at a wavelength of about 1.06 microns.
 3. fabricating a laser article from the glass blank, the article having increased lasing efficiency.
 3. A laser glass composition consisting essentially of:
 4. A laser glass host consisting essentially of about 67-87.8 mole percent TeO2, about 0.2-6 mole percent La2O3, and about 12-32.8 mole percent ZnO, the host composition containing about 0.01-1.5 mole percent Nd2O3.
 5. A laser glass composition as defined in claim 3 in which the host glass comprises about 70 mole percent TeO2, 27 mole percent ZnO, and 3 mole percent La2O3.
 6. A laser glass composition as defined in claim 3 in which the glass host comprises about 72 mole percent TeO2, 3 mole percent La2O3, and 25 mole percent ZnO.
 7. A laser glass composition as defined in claim 3 in which the glass host comprises about 68 mole percent TeO2, about 7 mole percent La2O3, and about 25 mole percent ZnO.
 8. A method for making a glass laser article such as a rod, disc and the like, the method comprising the steps of:
 9. A method as defined in claim 8 in which the glass comprising TeO2, La2O3 and ZnO has amounts thereof defined by the area within the triangle connecting the points EFGH of the ternary diagram of the Figure of the drawing.
 10. The new use for a TeO2/La2O3/ZnO glass composition as a glass laser article in which the proportions of TeO2, La2O3 and ZnO are defined by the area within the heavy lines connecting the points ABCD in the ternary diagram in the Figure of the drawings and in which the glass composition is a host for an effective lasing amount of Nd2O3, the new use comprising the steps of:
 11. A laser glass article made from the composition defined in claim
 1. 12. An article as defined in claim 11 in the form of a rod.
 13. An article as defined in claim 11 in the form of a disc.
 14. A laser glass article made according to the composition defined in claim 1 in which the laser glass composition has the proportions of TeO2, La2O3 and ZnO that are within the area formed by the heavy lines connecting the points EFGH in the ternary diagram of the figure of the drawing. 